4 - Kinetics of Emulsion Polymerization

Kinetics of Emulsion Polymerization
Professor José M. Asua
Institute for Polymer Materials (POLYMAT)

The University of the Basque Country
Donostia-San Sebastián, Spain
September 13, 2005
Emulsion Polymerization Processes Course

September 2005, Donostia-
Donostia-San Sebastián
Mechanisms Involved in Emulsion Polymerization
Initiator I*
+M
Monomer Droplet I *
Entry
Termination
Polymerization
Exit
+M M*
Entry
M
*
Entry
M*
Exit

Complex mechanisms Complex products
Initiator I* 0,8
Latex 2
Monomer +M 0,6
b30
0,4
Droplet
I *
0,2
0
3 4 5 6 7 8
logM
Entry
Termination • Polymer Composition
• CCD
• MWD
• Branching
Polymerization • Crosslinking
Exit • Gel content
M* • Particle morphology
+M • Particle size distribution
Entry
M
*
M*
Exit dp

Np= 1017 particles/L
particle 1
Representative particle
time
n ñ
particle 2
.
. time time
. n
Average
particle n number of
radicals
per particle
time

Polymerization Rate
ñ
r = kp[M] [ R] = kp[M] (mol/L s)
p p pN v part
A p
ñ ñ
Rpp = kp[M] v = kp[M] (mol/part s)
pN v p pN
A p A
ñ
Rp = kp[M]p Np (mol/s)
N
A

Polymerization Rate
Homopolymerization
Rp = k p[M]p ñ Np 


mol/s 
N
A
Copolymerization (2 monomers)
p p 
P  [i]p ñ Np


Rp =  k P +k 
 mol/s 
i  pAi A pBi B  N 
A* + i
B* + i
Probabilty of having a given ultimate unit in the growing chain
A* + B B* + A
kpAB [RA ][B]p = kpBA [RB ][A]p
P AP =
[R A ] = kp BA [ A ]P
[R A ] + [R B ] kp BA [A ]P + kp AB [B ]P
P BP = 1 − P AP

Polymer Particles Aqueous Phase
kp BA [A ]P kp BA [A ]w
P AP = P Aw =
kp BA [A ]P + kp AB [B ]P kp BA [A ]w + kp AB [B ]w
P BP = 1− P AP
PBw = 1 − P Aw
Different copolymer compositions in particles and aqueous phase

Reactivity Ratios
Ultimate model
kpAA
ABBBAA……..A* + A ABBBAA……..AA*
k p11 k p22
r1 = ; r2 =
k p12 k p21

Termination Rate Constant
Zero polymer content
Copolymerization (2 monomers)
p 2 p 2
kt o = kt o  P  + 2kt o P p P p + kt o  P 
 
11  1  12 1 2 22  2 

Diffusion controlled termination rate constants
kt = kt = kt = kt = kt = 4 π (D +D ) ra N
11 22 12 21 1 2 A
Di= diffusion coefficient

ra= radius of interaction
average gel effect chain length dependent
[ )]
D =D + Dp
kt = kt exp − aφ − b(φ
o p p 2 i im
= D mon /l α
p p
D
im i

Polymerization Rate
ñ
N
A

Radical Entry and Exit
Initiator I*
+M
Monomer Droplet I *
Entry
Termination
Polymerization
Exit
+M M*
Entry
M
*
Entry
M*
Exit

Effect of radical entry and exit on Rp and MWD
Polymerization rate: Entry ñ Rp
Exit ñ Rp
Molecular Weights:
chain length
entry termination Time
termination chain length
ñ (entry)
transfer
Radical Entry
Initiator * -
+M
*M -
+M
- *MM -
- -
+M
*MMM -
-
-
-
- -
-

Initiator * -
*M -
*MM -
2 fk [ I ] j *MMM -
[R ] = I ∏ α
j W k [M ] i
p w i =1 [Rj]w αi
k p [ M ]W
αi =
Np
k p [ M ]W + 2k t [ R]W + k ai φWW
NA
j

Monomer Removal
CH3
·
TBHP CH3 C O
HIDROFOBiCIty
CH3
H2O2 OH
·
KPS
-
O S O ·
O
Dr. María Paulis, Thrursday, September 15

Monomer removal
CH3
O
CH3 C O·
O·
-
O S +M
CH3
O
+M
IM· Particle
+…M
IMM·
Termination
IMz·

Monomer removal
Reductant: AsAc; Feeding time :1 hour

Latex VAc/BuA
1
0.8
0.6
VAc conversion
0.4
TBHP
HO
0.2 2 2
KPS
0
0 20 40 60 80 100 120 140
Time (min)
P. Ilundain et al., J. Polym. Sci., Part A: Polymer Chemistry 4245, 40 (2002)

- -
-
-
- *MMM -
-
- -
-
radicals
R ( j) = k [R ] ( )
entry aj j W particle s
4πD RN
Wj A
k =
aj D δ eΩ D
Wj 1 Wj eΩ
W '+ +
D R D m R η (coth R η − 1)
hj pj j
C Mj* s
mj =
C Mj*e

Surface potential
eψ 0
Ω=
kT
R +δ2 R +δ 2
 eψ 0  dr
W '= R ∫ exp  2
δ2 R  kT r

- -
-
-
- *MMM -
-
- -
-
radicals
R ( j) = k [R ] ( )
4πD RN
Wj A
k =
aj D δ eΩ D
Wj 1 Wj eΩ
W '+ +
hj pj j
C Mj* s
mj =
C Mj*e

- -
-
-
- *MMM -
-
- -
-
radicals
R ( j) = k [R ] ( )
4πD RN
Wj A
k =
aj D δ eΩ D
Wj 1 Wj eΩ
W '+ +
hj pj j
C Mj* s
mj =
C Mj*e

Styrene Vinyl acetate
* - Initiator * -
+M +M
*M - *M -
+M +M
*MM - - - *MM -
-
+M
- *MMM -
- +M
- *MMMM -
- -
- +M
*MMMMM -
• Low water solubility (3x10-4 g/100 g • Substantial water solubility (2.5g/100g
water; low growth rate in aqueous phase) water; high growth rate in aqueous phase)
• Big changes in oligomer water solubility • Moderate changes in oligomer water
by adding one monomer unit to the chain. solubility by adding one monomer unit to
the chain.
Propagational Entry
Styrene
* - Initiator
+M
*M -
+M - -
*MM - -
-
-
-
- -
-
NA
R = k [M] [R ]
entry p W z − 1 W N p ö WW
Maxwell et al. Macromolecules 24, 1629 (1991)

Acidic monomers in the formulation
A* M* *M - *A -
- -
AM* MA* MM* AA*
- *MA - *MM -
*AM - *AA -
-
MMM* MMA* MAM* - *MMM - *AAA -
-
AMM* AAM* MAA* - - *MAM - *AMM -
AMA* AAA* - *MMA - *AAM -
*MAA - *AMA -
Chains are very different, therefore entry rate of each chain is different

High surface charge density
-
- -
- -
- -
-
--
-- - - -
-- -
- -
- -
-- - - -
--
Cheong & Kim, Colloids and Surfaces A, 153, 137 (1999)

Strong resistance of the electrosteric hairy layer
Cohen et al. Macromolecules 29, 5128 (1996)

1
One order of magnitude reduction in entry rate
Rentry pH=7<< Rentry pH=4
- --
0.8
- -
0.6 - --
Vorwerg-Gilbert, Macromolecules 33, 6693 (2000)
0.4
Entry rate reduced in lesser extent
- -
-- ---
--- - ---
0.2
-
0
4
1 10 100 1000 10
D /D
w h

Radical Entry: Summary
Entry of short oligomers with hydrophilic end groups is difficult
Initiators yielding hydrophobic radicals are more efficient under

conditions in which [M]w is low (starved conditions, monomer
postpolymerization).
Oligoradicals of different lengths may significantly contribute to

the overall entry rate.
The general model contains too many parameters
A pragmatic approximation is to represent the rate of entry as:
ka[R]w
ka being an adjustable parameter.

Radical Exit
Initiator I*
+M
Monomer Droplet I *
Entry
Termination
Polymerization
Exit
+M M*
Entry
M
*
Entry
M*
Exit

Mechanisms for Radical Exit
Diffusion
Propagation
M* M* Termination
Polymerization
+M chain
transfer Reentry
*
rate of radical diffusion

Rexit = Rate radical formation (1 − reentry) = k d ñN p
rate of propagation

surfactant
layer
stagnant
δ2 δ1 liquid film
CM*
CM*s
m C M *s
Styrene 2000 m=
Vinyl acetate 29
CM*e C M *e
CM*w
CM*h

R = k d ñN p
exit
λN A λNp
kd = γ (1 − ) (s -1 )
ηm λNp + k p [M ]w + 2k tw [R]w
1
γ = ( k fm [M ] p
diffusion
) M* M*
vpNA
η = k p [M ] p
polymerization
λ = Rate of diffusion +M chain
transfer
reentry
*
C M *s
m=
C M *e
Asua, Macromolecules, 36, 6245 (2003)
0.1
Np=6x1015 particles/L
0.01
0.001
0.0001
10 100 1000
R (nm)

0.1
- --
- -
- --
0.01
- -
-- ---
--- ---
- -
R = 50 nm
Np = 6x1015 particles/L
0.001
10-11 10-10 10-9 10-8 10-7 10-6
2
D (dm /s)
h
Coen, E.M.; Lyons R.A.; Gilbert, R.G.; Macromolecules, 1996, 29, 5128.
Vorwerg, L.; Gilbert, R.G.; Macromolecules, 2000, 33, 6693.
0.1
R = 50 nm
k p [M ]w + 2k tw [R]w < λNp

0.01
0.001
0.0001
0 0.1 0.2 0.3 0.4 0.5 0.6
solids content

0.1
0.01
0.001
0.0001
R = 50 nm
solids content = 50 wt%
10-5
10-10 10-9 10-8 10-7 10-6 10-5 0.0001
R (mol/L)
w

Radical exit: Summary
kd = f ( kfm, [M]p, kp, ktp, Dp, Dh, Dw, R,

Np, initiator type and concentration, solids content, ktw, [M]w )
Practical consequence: kd determined under some given experimental

conditions cannot be directly used to predict the behavior of
emulsion polymerization systems under different conditions.

Polymerization Rate
ñ
N
A

Average Number of Radicals per Particle
particle 1
Representative particle
time
n ñ
particle 2
.
. time time
. n
particle n
∑ nN n
ñ=
∑ Nn
time

Average Number of Radicals per Particle
Initiator I*
+M
Monomer Droplet I *
Entry
Termination
Polymerization
Exit
+M M*
Entry
M
*
Entry
M*
Exit

Entry rate:
 radicals 
k [R]  particle time 
a w  
Exit rate:
 radicals 
k n  particle time 
d(n)  
Termination rate:
n − 1 v N = 2 k t n(n − 1) = 2cn(n − 1)

2k n 

radicals 
t vpN vpN p A vpN 
particle time 
A A A 

Population Balance of Nn
dNn = k [R] N
a w n − 1 + k d(n + 1)(n + 1)Nn + 1 + c(n + 2)(n + 1)Nn + 2
dt
Termination in Nn+2
Entry in Nn-1 Exit from Nn+1
− k a[R]w Nn − k nN − cn(n − 1)Nn n=0,1,2,3,…..

d(n) n
Entry in Nn Exit from Nn Termination in Nn

Approximate solution for ñ (dNn/dt=0)
2ka[R]w
ñ=
0.5
k +  k 2 + 4ka[ R]wcf 

d  d 
2 2ka[R]w + k 
f=  d
2ka[R]w + k + c
d
kt
c=
vpN
A
d[R]w Np Np
= 0 = 2fk I [I] + k dñ − 2k tw [R]2w − k a [R]w
dt N A Vw N A Vw
Li and Brooks, J. Polym. Sci. Part A: Polym. Chem., 31, 2397 (1993)
2k cN V
Y= tw A w = 0 Smith-Ewart limiting cases
k a2 Np
Case 1: ñ<<0.5
2fk IN k a [R]w
I A ñ=
αw = 2k a [R]w + k
cNp d
k Case 2: ñ=0.5
m= d
c Case 3: ñ>>0.5
 2fk IN 
12
ñ =  I A 
 2cNp 
 
J. Ugelstad, F.K. Hansen, Rubber Chem. Technol., 49, 536 (1976)

2k cN Vw
Y = tw A = 0 Smith-Ewart limiting cases
ka2Np
Case 1: ñ<<0.5
small particles (<100nm);
water-soluble monomers/CTA
2fk IN small amount of initiator
αw = I A many polymer particles
cNp
Case 2: ñ=0.5
k water-insoluble monomers
m= d no chain transfer reactions
c rapid termination rate
dp < 200 nm
Case 3: ñ>>0.5
large particles (>200 nm)
high amount of initiator (redox)
slow termination rate (gel effect)

2k cN Vw
Y = tw A = 0
ka2Np
n
ñ = 0.5 ⇒ Rp ÷ Np; Mw ÷ Np
2fk IN
αw = I A
cNp
k
m= d
c

2k cN Vw
Y = tw A = 0
ka2Np
2fk IN
αw = I A ñ÷ 1
Np
⇒ Rp ≠ Np; Mw = bulk
cNp n
k
m= d
c time

n Mw = chain transfer
time
2k cN Vw
Y = tw A = 0
ka2Np
k
m= d
c
2fk IN
αw = I A
cNp Course
Emulsion Polymerization Processes
2k cN Vw
Y = tw A = 0
ka2Np
2fk IN
αw = I A
cNp
k
m= d
c

Polymerization Rate
ñ
Rp = kp[M] Np (mol/s); (mol/L s)
pN water
A

Monomer Concentration in the Polymer Particles
M
S2O8=
S2O8= M
Monomer
droplet M
M

Mass Transfer vs. Polymerization Rate
Monomer Aqueous Polymer

droplets phase particles
[M]d Diffusion>>Rp [M]p = [M]p(eq)
[M]w
Diffusion < Rp [M]p < [M]p(eq)
Mass transfer limitations:

•Droplet-water interface
•Poor emulsification of water-insoluble monomers
•Preemulsification minimizes this effect

EXAMPLE OF MASS TRANSFER LIMITATIONS
[M] p
[CTA] p
1
0.7 process 0.8

300 rpm
0.6
0.6
0.5
0.4 0.4
0.3
0.2
Anchor
0.2
0.1 0
3.5 4 4.5 5 5.5 6 6.5 7
0 log Mw
3.5 4 4.5 5 5.5 6 6.5 7
log Mw
0.7
0.6
Desired
X=0.18
0.6 400 rpm
0.5
X=0.47 0.5
0.4 X=0.60
X=0.77 Preemulsified 0.4
0.3 X=0.96 feed 0.3
0.2 0.2
0.1
Fluidfoil
0.1
0
0.0
3.5 4 4.5 5 5.5 6 6.5 7
3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 log Mw
log (D)
Partitioning under Thermodynamic Equilibrium
[M]p
Monomer
[M]
Monomer

Homopolymerization. No monomer droplets
Morton equilibrium equation:
w 


 Φ


 p p    p  2  2Vmγ

RTln M
  = RTlnΦ + Φ 1 − 1  + χ  Φ   +
 
Φ

W 



M p Dp   p 
 r
   
Msat 

Φp + Φp = 1
Material balances:
M pol
Φw + Φw =1
W M
w
Vw Φ = W
W
VpΦ p = V
pol pol
VpΦ p + Vw Φ w = V
M M M
Homopolymerization. Monomer droplets
if : Φw = ΦW
M Msat
 p  p   p  2  2Vmγ
0 = RT lnΦ + 1 − Φ 1 − 1 Dp  + χ 1 − Φ   +
 M  M    M 
  r
[M]p
χ γ
dp dp

Homopolymerization. Monomer droplets. Crosslinked polymers
  p 

p p  p 2 V ρ  1 Φ
    m p   p  3 p  2Vmγ
0 = RT lnΦ + Φ 1 − 1  + χ Φ  +
 Φp  − +


M p Dp   p  M c  
 2  r
 
   
Molecular weight
between crosslinks
[M]p
Mc
dp

Homopolymerization. No monomer droplets
Partition coefficients:
p
p Φ Does not include effects of
K = M particle size and interfacial tension
M Φw
M
Material balances:
Φp + Φp = 1
M pol
Φw + Φw =1
W M
Vw Φ w = W
W
VpΦ p = V
pol pol
VpΦ p + Vw Φ w = V
M M M
Homopolymerization. Monomer droplets
Partition coefficients:
p p w
Φ M = K Φ Msat
M

Copolymerization
p
p Φ Φd
Equilibrium equations: K = 1 Kd = 1
1 Φw 1 Φw
1 1
p
p Φ Φd
K = 2 Kd = 2
2 Φw 2 Φw
2 2
Material balances:
Φp + Φp + Φp = 1 VpΦ p + Vw Φ w + V Φd = V
1 2 pol 1 1 d 1 1
Φw + Φw + Φw w =1 VpΦ p + Vw Φ w + V Φd = V
1 2 2 2 d 2 2
w
Vw Φ w = W
Φd + Φd = 1
1 2
VpΦ p = V
pol pol

A guide for the choice of the partitioning model
Criterion: Simplest but sufficiently accurate model
Batch emulsion polymerization:

Morton model: low solids content (10wt%)
unseeded medium solids content (30wt%)
completely water-soluble monomers
Constant partition coefficients:
seeded medium solids content
seeded and unseeded high solids content (55wt%)
Semicontinuous emulsion polymerization (starved conditions)

Morton model: low solids content
high solids content
Semicontinuous emulsion polymerization (nonstarved conditions)

Morton model: water soluble monomers
low solids content
high solids content
Gugliotta et al. J. Appl. Polym. Sci., 55, 1017 (1995)

Complex mechanisms Complex products
Initiator I* 0,8
Latex 2
Monomer +M 0,6
b30
0,4
Droplet
I *
0,2
0
3 4 5 6 7 8
logM
Entry
Termination • Polymer Composition
• CCD
• MWD
• Branching
Polymerization • Crosslinking
Exit • Gel content
M* • Particle morphology
+M • Particle size distribution
Entry
M
*
M*
Exit dp

Further reading:
Copolymerization
F.R. Mayo, F.M. Lewis, J. Am. Chem. Soc., 66, 1594 (1944).
J. Forcada, J.M. Asua, J. Polym. Sci.. Polym. Chem. Ed., 23, 1955 (1985).
M.L. Coote, T.P. Davis, Prog. Polym. Sci., 24, 1217 (1999).
J.R. Leiza, J.M. Asua, Copolymers, Kirk-Othmer Encyclopedia of Chemical Technology, on-line version.
Diffusion controlled kt (Gel Effect)

I.A. Maxwell, G.T. Russell, Makromol. Chem. Theory Simul. 2, 95 (1993).
N. Friis, A.E. Hamielec, in Emulsion Polymerization, I. Piirma , J.L. Gardon Eds., ACS Symp. Ser., 24, (1976)
Radical entry
F.K. Hansen and J. Ugelstad, J. Polym. Sci., Polym. Chem. Ed., 16, 1953 (1978)
I.A. Maxwell, B.R. Morrison, D.H. Napper, R.G. Gilbert, Macromolecules, 24, 1629 (1991)
Radical exit
J.M. Asua, Macromolecules, 36, 6245 (2003)
Average number of radicals per particle

Li and Brooks, J. Polym. Sci. Part A: Polym. Chem., 31, 2397 (1993)
Monomer Partitioning
M. Morton, S. Kaizerman, M. W. Altier, J. Colloid Sci., 9, 300 (1954)
J. Ugelstad et al., in Science and Technology of Polymer Colloids, G.W. Poehlein, R.H. Ottewill,J.W. Goodwin,
Eds., NATO ASI Ser., Ser. E 1983.
L.M. Gugliotta, G. Arzamendi, J.M. Asua, J. Appl. Polym. Sci, 55, 1017 (1995)


4 - Kinetics of Emulsion Polymerization

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4 - Kinetics of Emulsion Polymerization

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Kinetics of Emulsion Polymerization

Professor José M. Asua

Institute for Polymer Materials (POLYMAT)

September 13, 2005

Emulsion Polymerization Processes Course

Mechanisms Involved in Emulsion Polymerization

Emulsion Polymerization Processes Course

Emulsion Polymerization Processes Course

Np= 1017 particles/L

Emulsion Polymerization Processes Course

Emulsion Polymerization Processes Course

kpAB [RA ][B]p = kpBA [RB ][A]p

Emulsion Polymerization Processes Course

Polymer Particles Aqueous Phase

Different copolymer compositions in particles and aqueous phase

Emulsion Polymerization Processes Course

Emulsion Polymerization Processes Course

Termination Rate Constant

Zero polymer content

Emulsion Polymerization Processes Course

Di= diffusion coefficient

average gel effect chain length dependent

Emulsion Polymerization Processes Course

Emulsion Polymerization Processes Course

Emulsion Polymerization Processes Course

Effect of radical entry and exit on Rp and MWD

Polymerization rate: Entry ñ Rp

entry termination Time

termination chain length

Emulsion Polymerization Processes Course

Emulsion Polymerization Processes Course

Dr. María Paulis, Thrursday, September 15

Emulsion Polymerization Processes Course

Emulsion Polymerization Processes Course

Reductant: AsAc; Feeding time :1 hour

P. Ilundain et al., J. Polym. Sci., Part A: Polymer Chemistry 4245, 40 (2002)

Emulsion Polymerization Processes Course

Emulsion Polymerization Processes Course

Emulsion Polymerization Processes Course

Emulsion Polymerization Processes Course

Emulsion Polymerization Processes Course

Styrene Vinyl acetate

Emulsion Polymerization Processes Course

Acidic monomers in the formulation

Emulsion Polymerization Processes Course

Cheong & Kim, Colloids and Surfaces A, 153, 137 (1999)

Emulsion Polymerization Processes Course

Strong resistance of the electrosteric hairy layer

Cohen et al. Macromolecules 29, 5128 (1996)

Emulsion Polymerization Processes Course

Entry of short oligomers with hydrophilic end groups is difficult

Initiators yielding hydrophobic radicals are more efficient under

Oligoradicals of different lengths may significantly contribute to

The general model contains too many parameters

A pragmatic approximation is to represent the rate of entry as:

ka being an adjustable parameter.

Emulsion Polymerization Processes Course

rate of radical diffusion

Emulsion Polymerization Processes Course

Emulsion Polymerization Processes Course

Emulsion Polymerization Processes Course

k p [M ]w + 2k tw [R]w < λNp